KR20190025221A - Manufacturing method of water treatment filter media for biofilm prevention - Google Patents

Abstract

The present invention relates to a method for manufacturing a water treatment filter medium for inhibiting biofilm formation in which a water treatment filter medium is coated with an antimicrobial agent for inhibiting biofilm formation. The method comprises the steps of: washing the water treatment filter medium with water or alcohol; drying the filter medium primarily; coating a binder; washing the filter medium primarily; immersing the filter medium in a vanillin solution and fixing the vanillin; washing the filter medium secondarily; and drying the filter medium secondarily. Therefore, the present invention can enhance the efficiency of the stable water purification process since the biofilm formation is inhibited by coating the antimicrobial agent on the water treatment filter medium in which the biofilm formation by the microorganisms is inhibited, and the number of backwashing operation of the separation membrane and MMF can be greatly reduced.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing a water treatment filter medium for inhibiting biofilm formation,

The present invention relates to a method for producing a water treatment filter material for inhibiting biofilm formation, and more particularly, to a method for producing a water treatment filter material for inhibiting biofilm formation by coating an antimicrobial agent for inhibiting biofilm formation on a water treatment filter material.

The unique signaling pathway of the bacteria, called quorum sensing, is determined by the concentration of specific signaling molecules, including N-acyl-homoserine lactone (AHL), which each individual cell secretes during growth, It is a series of mechanisms that regulate cell density dependent gene expression.

That is, when the quorum sensing (QS) grows to a so-called " quorum ", in which the cell density is increased and reaches a certain cell density, The traits are collectively induced. Various traits are regulated by QS, and the formation of biofilm by bacterial bacteria, which is common in the surroundings, is a typical phenomenon controlled by QS.

In the QS process, some bacteria synthesize a signal molecule compound called AI (autoinducer) and secrete it out of the cell. The concentration of AI that accumulates with the growth becomes proportional to the density of bacteria. At this time, when the accumulated AI reaches a definite concentration, it diffuses into the cell again, binds to the receptor protein, and induces the expression of various target genes, ultimately changing the collective behavior of bacteria.

The biofilm is an extracellular polymeric matrix (EPM) that is attached to the surface of the microorganism and secreted outside the cell. The biofilm is likened to a kind of microbial city where many microbial species live together as a community, and thus the environment for the QS system to operate is established.

As most bacterial life cycles, biofilm formation has a series of distinctive cycles, with planktonic cells attaching to the surface, and formation of a monolayer by attached cells And microcolony formation, forming a mature biofilm with a typical three-dimensional structure in the form of a tower or mushroom.

After that, the biofilm is finally disintegrated and dispersed, and then it is returned to the suspended bacteria again.

A bioanalytical dissociation and dispersion method can be used to synthesize a signaling substance analogue by substituting carbon atoms in the lactone ring or acyl side chain of the AHL molecule, Instead, it binds competitively to the binding site of the QS receptor and disrupts the signal.

In particular, biofouling also occurs in anthropogenic systems such as pipes and tanks exposed to water for long periods of time, membrane bioreactors (MBR), etc., which degrade efficiency by corroding or contaminating the device. In particular, membrane systems are increasingly used for wastewater treatment and drinking water production, but the biofouling phenomenon in the membrane remains a problem in the process.

Since QS plays a key role in the formation of biofilm as described above, it is possible to inhibit the formation of the biofilm formed on the surface of the membrane if QS, which is a signal transmission system of aquatic bacteria, can be blocked. Therefore, As a new attempt to control.

To inhibit the formation of biofilms, we have developed synthetic QS inhibitors such as furanone and vanillin (4-hydroxy-3-methoxybenzaldehyde), which act on AHL receptors, as well as natural products such as furanone derivatives Research is most actively carried out. AHL degrading enzymes can also be used to inhibit biofouling.

In MBR separation process for wastewater treatment, biofouling due to formation of biofilm during operation causes problems such as decrease in permeability. In order to solve this problem, it was reported that porcine kidney acylase I QQ (quorumquenching) enzyme treatment in MBR process for wastewater treatment decreased membrane contamination and decreased pressure between membranes compared to the control .

In order to enhance the biofouling inhibition effect of QQ enzyme in wastewater, Rhodococcus sp. The isolate was isolated, and as a result of applying MBR using this isolate, it is known that membrane contamination is reduced and membrane permeability is improved.

Open No. 10-2015-0137299 discloses a process for producing a reverse osmosis membrane filter for inhibiting the formation of biofilm comprising the steps of adding epigallocatechin gallate (EGCG) and aminopropylisobutyl polyhedral oligomeric silsesquioxane ("POS" The synthesized POSS-EGCG antimicrobial substance was impregnated into the reverse osmosis membrane to confirm the biofilm inhibiting effect.

However, when the biofilm inhibiting material is coated on the above-described separation membrane, the size of the micropores of the separation membrane is reduced, and the water permeability is significantly lowered, so that normal water purification is not easy.

Korean Patent No. 10-0249421 (Mar. 15, 2000) Korean Patent Publication No. 10-2004-0040038 (May 12, 2004) Korean Patent No. 10-1203691 (November 23, 2012)

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the above-mentioned conventional problems, and it is an object of the present invention to provide a membrane- It is an object of the present invention to provide a method for producing a water treatment filter material for inhibiting biofilm formation which can increase the efficiency of a stable water purification process.

In addition, the present invention dramatically reduces the frequency of backwash operation to recover membrane clogging due to biofilm formation due to microbial aggregation on the surface of the membrane by inducing inhibition of biofilm formation in the MMF process before membrane separation, And a method for producing a water treatment filter material for inhibiting biofilm formation.

The present invention also provides a method for manufacturing a water treatment filter material for inhibiting biofilm formation which can significantly improve the operation life of a water treatment apparatus using membrane separation by inhibiting biofilm formation due to microbial aggregation by a multi-layer filtration system water treatment filtration apparatus For another purpose.

According to an aspect of the present invention, there is provided a method for manufacturing a water treatment filter material for inhibiting the formation of an biofilm, the method comprising: washing a water treatment filter material with water or alcohol; Drying the washed water treatment filter material in a drier; Immersing the dried water treatment filtration material in a binder solution and reacting in a reactor to coat the binder; Washing the binder which has not reacted with the reacted water treatment filter material with an alcohol or organic solvent; Immersing the washed water treatment filter material in a vanillin solution and reacting in the reactor to fix the vanillin; Washing the vanillin which has not reacted with the reacted water treatment filter material with an alcohol or an organic solvent; And secondly drying the washed water treatment filter material in a drier.

In the primary drying step of the present invention, the water treatment filter material is dried in a drier at 80 to 250 캜 for 1 to 24 hours.

In the binder coating step of the present invention, the water-soluble filter medium is immersed in a solution of the binder dissolved in a concentration of 0.1 to 3 mol, and reacted in a reactor maintained at a temperature of 25 ° C to 200 ° C for 0.5 to 24 hours to form a binder .

Examples of the binder include APTMS (3-Aminopropyl) trimethoxysilane, APTES (3-Aminopropyl) triethoxysilane, GPTMS (3-Glycidyloxypropyl) trimethoxysilane, APS (3-Aminopropyl) triethoxysilane, AHAPS, MPMS, TPU, and the like.

The solution in which the binder of the present invention is dissolved is characterized by comprising a solution in which the aminosilane binder alone or in combination is dissolved in an organic solvent selected from methanol, ethanol, propanol and butanol or an alcohol solvent selected from toluene and nucleic acid .

In the vanillin fixing step of the present invention, vanillin dissolved in alcohol-based solvent or organic solvent dissolved in vanillin at a concentration of 0.1 to 3.0 mol is added to the first washed water treatment filter material, For 24 hours to fix the vanillin.

The water treatment filter material of the present invention is characterized by being composed of anthracite and sand.

As described above, according to the present invention, the biofilm formation is inhibited by coating the antibacterial agent on the water treatment filter material in which the biofilm formation by the microorganism is inhibited, and the number of backwash operation of the separation membrane and the MMF can be greatly reduced, And provides an effect that can be achieved.

In addition, it is more effective to inhibit the biofilm formation in the MMF process, which is the pre-membrane separation stage, than to induce the inhibition of biofilm formation by the microbial aggregation by coating an antimicrobial substance on the separation membrane by the efficiency improvement method of the wastewater water treatment process. The frequency of backwash operation for recovering the clogging phenomenon due to the biofilm formation is drastically reduced, thereby providing an effect of drastically improving the overall water treatment efficiency.

In addition, by using vanillin-coated anthracite and sand as a water treatment filtration material, the multi-layer filtration type water treatment filtration apparatus can suppress the biofilm formation due to microbial aggregation and greatly improve the operation life of the water treatment apparatus using membrane separation Lt; / RTI >

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a method for producing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention; FIG.
2 is a graph showing a binder used in a method for producing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention.
FIG. 3 is a diagram showing a vanillin used in a method for producing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention.
4 is a view showing a coating process of an antimicrobial agent in a method for producing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention.
5 is a graph comparing the state of antibacterial agent coated on the sand by the method of producing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention.
FIG. 6 is a graph comparing the state of anthracite coated with an antimicrobial agent by a method for producing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention. FIG.
FIG. 7 and FIG. 8 are graphs showing XPS analysis results of a vanillin-coated base material filter material by a method of producing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a flow chart showing a method of manufacturing a water treatment filter medium for inhibiting biofilm formation according to an embodiment of the present invention. FIG. 2 is a cross- sectional view of a binder used in a method of manufacturing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention. FIG. 3 is a diagram showing vanillin used in a method for producing a water treatment filter medium for inhibiting biofilm formation according to an embodiment of the present invention. FIG. FIG. 5 is a graph comparing the state of the antibacterial agent coated on the sand by the method for producing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention , FIG. 6 is a graph showing the results of measurement of anthracite by the method of manufacturing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention FIG. 7 and FIG. 8 are graphs showing XPS analysis results of vanillin-coated base material filter material by a method of manufacturing a water treatment filter material for inhibiting biofilm formation according to an embodiment of the present invention. Graph.

As shown in FIG. 1, the method for manufacturing a water treatment filter material for inhibiting biofilm formation according to the present embodiment includes a filter material washing step S10, a primary drying step S20, a coating step S30, a first washing step S40 ), A reaction step (S50), a secondary washing step (S60), and a secondary drying step (S70). The biofilm formation process is performed by coating an antimicrobial agent for inhibiting biofilm formation on a water treatment filter material such as MMF Water treatment filtration material for inhibition.

This water treatment filter material is composed of anthracite and sand, and the sand used as the MMF filter material is mainly composed of silica (SiO ₂ ). On the sand surface, there is a small amount of hydroxyl group (-OH) Anthracite has various surface functional groups such as a phenol group (-OH) and a carboxyl group (COOH) on its surface.

The filter material washing step (S10) is a step of washing the water treatment filter material with water or alcohol. In the process of removing the floating material particles by the multi-media filtering method (MMF) which is one of the floating material particles removal process in the water treatment process, Anthracite and sand, which are mainly used as water treatment filters, are washed.

The first drying step (S20) is a step of drying the water treatment filter material washed in the filter material washing step (S10) by a dryer, and drying the water treatment filter material in a drier at 80 to 250 캜 for 1 to 24 hours desirable.

The coating step S30 is a step of immersing the water treatment filter material dried in the primary drying step S20 in a binder solution and reacting the binder in a reactor to form a binder. The binder solution is dissolved in a concentration of 0.1 to 3 mol, And then reacted in a reactor maintained at a temperature of 25 ° C to 200 ° C for 0.5 to 24 hours to coat the binder.

These binders include APTMS (3-Aminopropyl) trimethoxysilane, APTES (3-Aminopropyl) triethoxysilane, GPTMS (3-Glycidyloxypropyl) trimethoxysilane, APS (3-Aminopropyl) triethoxysilane, AHAPS (n- 6-aminohexyl) -aminopropyltrimethoxysilane, MPMS, and Thermoplastic Polyurethane (TPU).

Particularly, as shown in FIG. 2, after the silane-based binders APTMS, APTES, APREMS and GPTMS are fixed to the surface hydroxyl groups of the sand and the anthracite, the amine groups (-NH ₂ ) at the ends of the silane- It is possible to produce an MMF filter material capable of inhibiting biofilm formation by vanillin-fixed or coated microorganisms by reacting with vanillin.

The solution in which the binder is melted is preferably a solution obtained by dissolving a binder in which an aminosilane-based binder alone or in combination is dissolved in an organic solvent selected from methanol, ethanol, propanol and butanol, or an organic solvent selected from toluene and nucleic acids.

The first washing step (S40) is a first washing step of a binder which has not reacted with the water treatment filter material reacted to be coated in the coating step (S30) with an alcohol or an organic solvent. The unreacted binder is washed .

The reaction step S50 is a step of immersing the washed water treatment filter material in the first washing step S40 in a vanillin solution and reacting the vanillin in the reactor to fix the vanillin. In the first washing step S40, The vanillin is immersed in an alcohol solvent or an organic solvent in which the vanillin is dissolved in a concentration of 0.1 to 3.0 mol and reacted in a reactor maintained at a temperature of 25 ° C to 200 ° C for 1 hour to 24 hours to fix the vanillin.

Therefore, as shown in Figs. 2 to 4, vanillin itself does not easily react with the sand and the anthracite surface stably and is not easily adhered or coated. Therefore, a binder for coating vanillin, which is an antimicrobial substance, on the surface of sand or anthracite (FIG. 2) and vanillin (FIG. 3) that can be applied safely by the use of the compound and an example of a reaction pathway using them (FIG. 4).

The second washing step (S60) is a second washing step of the vanillin which has not reacted with the water treatment filter material reacted in the reaction step (S50) with an alcohol or an organic solvent. After completion, the vanillin-free anhydrous ethanol solution And then washed twice with anhydrous ethanol.

The second drying step (S70) is a step of drying the washed water treatment filter material in the second washing step (S60) by a dryer, wherein the washed vaniline fixed sand filter material and the anthracite filter material are respectively dried in a dryer at 120 DEG C And dried for 12 hours to prepare vanillin-coated sand filter media and anthracite filter media for inhibiting biofilm formation of the MMF process, respectively.

Accordingly, the present invention relates to an anthracite and sand water treatment filter medium used as a filter medium in a process of removing suspended particles by a multi-media filter (MMF) of a water treatment apparatus, (Vanillin) coatings.

In addition to the sand and anthracite provided in the present embodiment, the MMF filter material used in the present invention can be applied to gravel, silica sand, activated carbon, sulfurized carbon fiber, porous silica, garnet, diamond stone and the like.

[Example 1]

Hereinafter, examples in which vanillin-coated sand filter media and anthracite filter media for inhibiting the biofilm formation in the MMF process are produced will be described in detail.

(One). Sand filter media with a diameter of 1-2 mm and anthracite were washed with anhydrous ethanol, respectively, and then dried in a dryer at 120 ° C for 24 hours.

(2). The dried sand filter media and anthracite were placed in a reactor which was refluxed with cooling water, and an anhydrous ethanol solution containing APTMS, one of aminosilane compounds of 1 mol concentration, was added thereto and reacted at 80 ° C for 6 hours.

Through this reaction, APTMS is immobilized on the -OH hydroxyl group of the surface of sand and anthracite filter media, respectively. As the silane compound used herein, aminosilane compounds such as APTES, APTMS, AHAPS, AEAPS, GPDES, MPMS, TPU and the like can be used.

In addition to anhydrous ethanol used as a solvent, solvents such as anhydrous methanol, hexane, and toluene can be used.

(3). After the reaction of (2) was completed, the unreacted APTMS-containing anhydrous ethanol solution supernatant was removed and washed twice with anhydrous ethanol.

(4). The immersed sand filter media and the anthracite filter media in (3) were immersed in a reactor which was refluxed with cooling water, and anhydrous ethanol solution containing 1 mol of vanillin was added thereto, followed by reaction at 80 ° C for 6 hours. At this time, vanillin reacts with the amino group of the aminosilane compound fixed by the reaction of (2) and is fixed.

(5). After the reaction of (4) was completed, the unreacted vanillin-containing anhydrous ethanol solution was removed, and then washed twice with anhydrous ethanol.

(6). The washed vanillin-fixed sand filter media and the anthracite filter media of (5) were placed in a dryer at 120 ° C for 12 hours, respectively, to prepare vanillin-coated sand filter media and anthracite filter media for inhibiting biofilm formation in the MMF process.

[Example 2]

Hereinafter, the degree of coating of vanillin-coated sand filter media and anthracite filter media for inhibiting biofilm formation in the MMF process is checked.

(One). In order to check the degree of coating of the binder and vanillin, the weight loss of uncoated sand, anthracite and vanillin coated sand and anthracite were measured by using a thermogravimetric analyzer (TGA).

5 and 6 show the weight loss measurement results obtained by raising the temperature from 30 ° C to 650 ° C at a rate of 2 ° C / min for each sample. It was confirmed that vanillin-coated sand prepared by the method of Example 1 and anthracite were coated as a weight ratio of the difference in the amount of the carbon compound decomposed at 120 ° C and 500 ° C, Respectively.

Type of filter media Name of sample Weight loss sand SD-non 0.13 wt% SD-C-120 0.83 wt% Anthracite AC-non 1.72 wt% AC-C-120 3.10 wt%

5 and 6 show TGA results of vanillin-free sand (SD-non) and vanillin-coated sand (SD-C-120) as a result of confirming vanillin coating degree using TGA, FIG. 6 shows the TGA test results of vanillin-coated anthracite (AC-non) and vanillin coated anthracite (AC-C-120).

(2). Suppression of vanillin-coated biofilm formation by photoelectron spectroscopy (XPS)

The coating state of the vanillin-coated sand and the anthracite, which are water filtering MMF media for inhibiting the biofilm formation by the membrane separation prepared by the method of Example 1, was measured using XPS (PHI 5000 VersaProbe (Ulvac-PHI) The analysis results show the results of C 1s and Si 2p peaks and the urea peaks of vanillin-coated sand filter media are shown in FIGS. 7 and 8.

7 and 8 are graphs showing the results of XPS peaks of the MMF sand filter media for inhibiting vanillin coating biofilm formation and FIG. 7 is a graph showing the binding energy of C-Si of APTMS as a binder in C 1s peak of vanillin- (283.5 eV), bonding energy of -OC = O (289 eV), and SiO ₂ peak (103.0 eV) as well as SiO ₂ C (102.5 eV) and SiO ₂ C ₂ (101.0 eV) peak, indicating that the sand is coated with a binder (APTMS) and vanillin.

As shown in the following Table 2, in the vanadium-coated sand filter media, the carbon content in the vaniline-coated sand and the silicon content in the anthracite are also increased .

Table 2 shows an example of the XPS analytical element content of vanillin-coated biofilm formation-inhibiting MMF filter media.

Type of MMF filter media Name of sample Atomic Concentration Ratio (%) C O Al Si Fe sand SD-non 17.47 60.51 7.77 12.08 2.16 SD-C-120 18.22 54255 3.08 21.58 - Anthracite AC-non 82.58 14.66 - 1.43 - AC-C-120 76.76 18.74 - 2.78 -

As described above, according to the present invention, by coating an antimicrobial agent on a water treatment filter material in which biofilm formation by microorganisms is suppressed, biofilm formation can be suppressed, and the number of backwash operations of the separation membrane and MMF can be greatly reduced, And provides an effect that can be achieved.

In addition, it is more effective to inhibit the biofilm formation in the MMF process, which is the pre-membrane separation stage, than to induce the inhibition of biofilm formation by the microbial aggregation by coating an antimicrobial substance on the separation membrane by the method of increasing the efficiency of the wastewater treatment process. The frequency of backwash operation for recovering the clogging phenomenon due to the biofilm formation is drastically reduced, thereby providing an effect of drastically improving the overall water treatment efficiency.

In addition, by using vanillin-coated anthracite and sand as a water treatment filtration material, the multi-layer filtration type water treatment filtration apparatus can suppress the biofilm formation due to microbial aggregation and greatly improve the operation life of the water treatment apparatus using membrane separation Lt; / RTI >

The present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. Therefore, the above embodiments are merely illustrative in all respects and should not be construed as limiting.

Claims (7)

A process for producing a water treatment filter material for inhibiting biofilm formation by coating an antimicrobial agent for inhibiting biofilm formation on a water treatment filter material,
Washing the water treatment filter with water or alcohol;
Drying the washed water treatment filter material in a drier;
Immersing the dried water treatment filtration material in a binder solution and reacting in a reactor to coat the binder;
Washing the binder which has not reacted with the reacted water treatment filter material with an alcohol or organic solvent;
Immersing the washed water treatment filter material in a vanillin solution and reacting in the reactor to fix the vanillin;
Washing the vanillin which has not reacted with the reacted water treatment filter material with an alcohol or an organic solvent; And
And drying the washed water treatment filter material in a dryer in a second step of drying the washed water treatment filter material. The method according to claim 1,
Wherein in the primary drying step, the water treatment filter material is dried in a drier at 80 to 250 캜 for 1 to 24 hours. The method according to claim 1,
In the binder coating step, the binder is coated by immersing the binder in an aqueous solution having a concentration of 0.1 to 3 mol and immersing the water-filtering medium in a reactor maintained at a temperature of 25 ° C to 200 ° C for 0.5 to 24 hours By weight based on the weight of the filtrate. The method of claim 3,
Examples of the binder include APTMS (3-Aminopropyl) trimethoxysilane, APTES (3-Aminopropyl) triethoxysilane, GPTMS (3-Glycidyloxypropyl) trimethoxysilane, APS (3-Aminopropyl) triethoxysilane, AHAPS, MPMS, TPU Of the aminosilane-based material is used as the water-treating agent. The method of claim 3,
Wherein the solution in which the binder is melted is a solution obtained by dissolving a binder in an alcohol solvent selected from methanol, A method for producing a water treatment filter material for inhibiting the formation of water. The method according to claim 1,
In the vanillin fixing step, a solution of vanillin dissolved in alcohol-based solvent or organic solvent dissolved in vanillin at a concentration of 0.1 to 3.0 mol is added to the primary washed water treatment filter medium, and the solution is maintained at a temperature of 25 ° C to 200 ° C for 1 hour to 24 And reacting the reaction solution with water for a predetermined time to immobilize the vanillin. The method according to claim 1,
Wherein the water treatment filtration material is composed of anthracite and sand.

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